CA3103348A1 - Process for the preparation of lactide and polylactide mixture - Google Patents
Process for the preparation of lactide and polylactide mixture Download PDFInfo
- Publication number
- CA3103348A1 CA3103348A1 CA3103348A CA3103348A CA3103348A1 CA 3103348 A1 CA3103348 A1 CA 3103348A1 CA 3103348 A CA3103348 A CA 3103348A CA 3103348 A CA3103348 A CA 3103348A CA 3103348 A1 CA3103348 A1 CA 3103348A1
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- Prior art keywords
- lactide
- composition
- reactor
- polymerization
- process according
- Prior art date
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- 239000000203 mixture Substances 0.000 title claims abstract description 85
- JJTUDXZGHPGLLC-UHFFFAOYSA-N lactide Chemical compound CC1OC(=O)C(C)OC1=O JJTUDXZGHPGLLC-UHFFFAOYSA-N 0.000 title claims abstract description 84
- 238000000034 method Methods 0.000 title claims abstract description 76
- 229920000747 poly(lactic acid) Polymers 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 65
- 239000002685 polymerization catalyst Substances 0.000 claims abstract description 12
- 230000000379 polymerizing effect Effects 0.000 claims abstract description 6
- 238000007151 ring opening polymerisation reaction Methods 0.000 claims abstract description 5
- 238000002156 mixing Methods 0.000 claims description 15
- 239000003054 catalyst Substances 0.000 claims description 12
- 239000011541 reaction mixture Substances 0.000 claims description 12
- 230000003068 static effect Effects 0.000 claims description 11
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 4
- -1 2-methyl-ethyl Chemical group 0.000 description 24
- 239000004626 polylactic acid Substances 0.000 description 20
- 125000004432 carbon atom Chemical group C* 0.000 description 17
- 239000002904 solvent Substances 0.000 description 13
- 125000000217 alkyl group Chemical group 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 11
- 125000003118 aryl group Chemical group 0.000 description 10
- 150000001875 compounds Chemical class 0.000 description 9
- JJTUDXZGHPGLLC-IMJSIDKUSA-N 4511-42-6 Chemical compound C[C@@H]1OC(=O)[C@H](C)OC1=O JJTUDXZGHPGLLC-IMJSIDKUSA-N 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 239000003999 initiator Substances 0.000 description 8
- 239000000654 additive Substances 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 5
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 5
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 5
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 5
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 5
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 5
- 125000001424 substituent group Chemical group 0.000 description 5
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 5
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- JVTAAEKCZFNVCJ-REOHCLBHSA-N L-lactic acid Chemical compound C[C@H](O)C(O)=O JVTAAEKCZFNVCJ-REOHCLBHSA-N 0.000 description 4
- 239000003963 antioxidant agent Substances 0.000 description 4
- 235000006708 antioxidants Nutrition 0.000 description 4
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 4
- 239000003426 co-catalyst Substances 0.000 description 4
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 4
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 230000006641 stabilisation Effects 0.000 description 4
- 238000011105 stabilization Methods 0.000 description 4
- BOZRCGLDOHDZBP-UHFFFAOYSA-N 2-ethylhexanoic acid;tin Chemical compound [Sn].CCCCC(CC)C(O)=O BOZRCGLDOHDZBP-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- 125000001931 aliphatic group Chemical group 0.000 description 3
- 125000004429 atom Chemical group 0.000 description 3
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 125000004122 cyclic group Chemical group 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000010828 elution Methods 0.000 description 3
- 238000001125 extrusion Methods 0.000 description 3
- 238000004817 gas chromatography Methods 0.000 description 3
- 238000005227 gel permeation chromatography Methods 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 125000001183 hydrocarbyl group Chemical group 0.000 description 3
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- JJTUDXZGHPGLLC-ZXZARUISSA-N (3r,6s)-3,6-dimethyl-1,4-dioxane-2,5-dione Chemical compound C[C@H]1OC(=O)[C@H](C)OC1=O JJTUDXZGHPGLLC-ZXZARUISSA-N 0.000 description 2
- BYEAHWXPCBROCE-UHFFFAOYSA-N 1,1,1,3,3,3-hexafluoropropan-2-ol Chemical compound FC(F)(F)C(O)C(F)(F)F BYEAHWXPCBROCE-UHFFFAOYSA-N 0.000 description 2
- HBAQYPYDRFILMT-UHFFFAOYSA-N 8-[3-(1-cyclopropylpyrazol-4-yl)-1H-pyrazolo[4,3-d]pyrimidin-5-yl]-3-methyl-3,8-diazabicyclo[3.2.1]octan-2-one Chemical class C1(CC1)N1N=CC(=C1)C1=NNC2=C1N=C(N=C2)N1C2C(N(CC1CC2)C)=O HBAQYPYDRFILMT-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 229930182843 D-Lactic acid Natural products 0.000 description 2
- JVTAAEKCZFNVCJ-UWTATZPHSA-N D-lactic acid Chemical compound C[C@@H](O)C(O)=O JVTAAEKCZFNVCJ-UWTATZPHSA-N 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- 208000034530 PLAA-associated neurodevelopmental disease Diseases 0.000 description 2
- 238000001069 Raman spectroscopy Methods 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 229910052797 bismuth Inorganic materials 0.000 description 2
- 150000007942 carboxylates Chemical class 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 229940022769 d- lactic acid Drugs 0.000 description 2
- MWKFXSUHUHTGQN-UHFFFAOYSA-N decan-1-ol Chemical compound CCCCCCCCCCO MWKFXSUHUHTGQN-UHFFFAOYSA-N 0.000 description 2
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 238000007872 degassing Methods 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 150000001991 dicarboxylic acids Chemical class 0.000 description 2
- 239000010408 film Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 229940042795 hydrazides for tuberculosis treatment Drugs 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- WVDDGKGOMKODPV-UHFFFAOYSA-N hydroxymethyl benzene Natural products OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 2
- 239000004310 lactic acid Substances 0.000 description 2
- 235000014655 lactic acid Nutrition 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- MKUWVMRNQOOSAT-UHFFFAOYSA-N methylvinylmethanol Natural products CC(O)C=C MKUWVMRNQOOSAT-UHFFFAOYSA-N 0.000 description 2
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 230000000737 periodic effect Effects 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- ULWHHBHJGPPBCO-UHFFFAOYSA-N propane-1,1-diol Chemical compound CCC(O)O ULWHHBHJGPPBCO-UHFFFAOYSA-N 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 229910052718 tin Inorganic materials 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- NMRPBPVERJPACX-UHFFFAOYSA-N (3S)-octan-3-ol Natural products CCCCCC(O)CC NMRPBPVERJPACX-UHFFFAOYSA-N 0.000 description 1
- 125000003837 (C1-C20) alkyl group Chemical group 0.000 description 1
- 239000005968 1-Decanol Substances 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- WOFPPJOZXUTRAU-UHFFFAOYSA-N 2-Ethyl-1-hexanol Natural products CCCCC(O)CCC WOFPPJOZXUTRAU-UHFFFAOYSA-N 0.000 description 1
- OBETXYAYXDNJHR-UHFFFAOYSA-N 2-Ethylhexanoic acid Chemical compound CCCCC(CC)C(O)=O OBETXYAYXDNJHR-UHFFFAOYSA-N 0.000 description 1
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 description 1
- DMLWITSKISPJIJ-UHFFFAOYSA-N 2-ethylhexan-1-olate Chemical compound CCCCC(CC)C[O-] DMLWITSKISPJIJ-UHFFFAOYSA-N 0.000 description 1
- 125000000094 2-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 1
- 241000219310 Beta vulgaris subsp. vulgaris Species 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- XBQGCGPTMHGUJX-UHFFFAOYSA-M CCO[Zn]OC1=C(CN(C)CCN(C)C)C=C(C(C)(C)C)C=C1C(C)(C)C Chemical compound CCO[Zn]OC1=C(CN(C)CCN(C)C)C=C(C(C)(C)C)C=C1C(C)(C)C XBQGCGPTMHGUJX-UHFFFAOYSA-M 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- 239000004386 Erythritol Substances 0.000 description 1
- UNXHWFMMPAWVPI-UHFFFAOYSA-N Erythritol Natural products OCC(O)C(O)CO UNXHWFMMPAWVPI-UHFFFAOYSA-N 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- JVTAAEKCZFNVCJ-UHFFFAOYSA-M Lactate Chemical compound CC(O)C([O-])=O JVTAAEKCZFNVCJ-UHFFFAOYSA-M 0.000 description 1
- 240000003183 Manihot esculenta Species 0.000 description 1
- 235000016735 Manihot esculenta subsp esculenta Nutrition 0.000 description 1
- 239000006057 Non-nutritive feed additive Substances 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 1
- 229930006000 Sucrose Natural products 0.000 description 1
- 235000021536 Sugar beet Nutrition 0.000 description 1
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical compound ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- 239000012963 UV stabilizer Substances 0.000 description 1
- 240000008042 Zea mays Species 0.000 description 1
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 1
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- BWVAOONFBYYRHY-UHFFFAOYSA-N [4-(hydroxymethyl)phenyl]methanol Chemical compound OCC1=CC=C(CO)C=C1 BWVAOONFBYYRHY-UHFFFAOYSA-N 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229920003232 aliphatic polyester Polymers 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- 125000001204 arachidyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000003934 aromatic aldehydes Chemical class 0.000 description 1
- 125000000732 arylene group Chemical group 0.000 description 1
- 125000004104 aryloxy group Chemical group 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 235000019445 benzyl alcohol Nutrition 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 125000002529 biphenylenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3C12)* 0.000 description 1
- 238000000071 blow moulding Methods 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- SHZIWNPUGXLXDT-UHFFFAOYSA-N caproic acid ethyl ester Natural products CCCCCC(=O)OCC SHZIWNPUGXLXDT-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 238000009264 composting Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 235000005822 corn Nutrition 0.000 description 1
- 230000002596 correlated effect Effects 0.000 description 1
- 150000003950 cyclic amides Chemical class 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 239000002274 desiccant Substances 0.000 description 1
- 239000012973 diazabicyclooctane Substances 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- UNXHWFMMPAWVPI-ZXZARUISSA-N erythritol Chemical compound OC[C@H](O)[C@H](O)CO UNXHWFMMPAWVPI-ZXZARUISSA-N 0.000 description 1
- 229940009714 erythritol Drugs 0.000 description 1
- 235000019414 erythritol Nutrition 0.000 description 1
- 230000007717 exclusion Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000011552 falling film Substances 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000010096 film blowing Methods 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- 150000004820 halides Chemical group 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- SXCBDZAEHILGLM-UHFFFAOYSA-N heptane-1,7-diol Chemical compound OCCCCCCCO SXCBDZAEHILGLM-UHFFFAOYSA-N 0.000 description 1
- 125000001072 heteroaryl group Chemical group 0.000 description 1
- 150000002391 heterocyclic compounds Chemical class 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 150000002429 hydrazines Chemical class 0.000 description 1
- 150000007857 hydrazones Chemical class 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 125000002960 margaryl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000004476 mid-IR spectroscopy Methods 0.000 description 1
- 230000003278 mimic effect Effects 0.000 description 1
- 239000012764 mineral filler Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004957 naphthylene group Chemical group 0.000 description 1
- 125000001196 nonadecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000002667 nucleating agent Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 125000002958 pentadecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 150000004707 phenolate Chemical class 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000003203 stereoselective catalyst Substances 0.000 description 1
- 238000000859 sublimation Methods 0.000 description 1
- 230000008022 sublimation Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229960004793 sucrose Drugs 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 238000003856 thermoforming Methods 0.000 description 1
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 1
- 125000002948 undecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 238000004260 weight control Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/06—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from hydroxycarboxylic acids
- C08G63/08—Lactones or lactides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/18—Stationary reactors having moving elements inside
- B01J19/1812—Tubular reactors
- B01J19/1837—Loop-type reactors
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/24—Stationary reactors without moving elements inside
- B01J19/2415—Tubular reactors
- B01J19/2435—Loop-type reactors
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
- C08G63/785—Preparation processes characterised by the apparatus used
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
- C08G63/82—Preparation processes characterised by the catalyst used
- C08G63/823—Preparation processes characterised by the catalyst used for the preparation of polylactones or polylactides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/15—Heterocyclic compounds having oxygen in the ring
- C08K5/156—Heterocyclic compounds having oxygen in the ring having two oxygen atoms in the ring
- C08K5/1575—Six-membered rings
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/00002—Chemical plants
- B01J2219/00027—Process aspects
- B01J2219/00033—Continuous processes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/00049—Controlling or regulating processes
- B01J2219/00051—Controlling the temperature
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/00049—Controlling or regulating processes
- B01J2219/00162—Controlling or regulating processes controlling the pressure
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
The invention relates to a process for the preparation of a composition comprising polylactide and lactide by ring-opening polymerization of lactide, said process comprising the steps of : (a) providing lactide and polymerization catalyst to a reactor, (b) melt polymerizing said lactide to a degree of polymerization of at most 96.0 %, to form a composition comprising polylactide and lactide, and (c) removing said composition from the reactor, wherein the whole process is performed at pressures of at least 1 bar, and wherein the composition removed from the reactor is never subjected to a pressure below 1 bar and wherein the composition is not subjected to one of more devolatilization steps.
Description
PROCESS FOR THE PREPARATION OF LACTIDE AND POLYLACTIDE MIXTURE
FIELD OF THE INVENTION
The invention relates to a process for the preparation of a composition comprising polylactide and lactide.
BACKGROUND OF THE INVENTION
Polylactide, also referred as polylactic acid (PLA), is a synthetic aliphatic polyester derived from renewable resources, such a cane sugar, corn, sugar beet and cassava, which can furthermore be degraded under industrial composting conditions. There is currently a need in the industry to provide mixtures of lactide and PLA. This notably concerns applications where the articles require faster degradation kinetics than pure PLA with minimal amounts of lactide. In these applications up to tens of percents of lactide may be required.
Currently, the industry can prepare these mixtures by compounding PLA with lactide monomer in a given ratio and then shaping the final mixture. There is therefore a need to improve the processes of the prior art.
SUMMARY OF THE INVENTION
In a first aspect, the present invention concerns a process for the preparation of a composition comprising polylactide and lactide by ring-opening polymerization of lactide, said process comprising the steps of: (a) providing lactide and polymerization catalyst to a reactor, (b) melt polymerizing said lactide to a degree of polymerization of at most 96.0 %, to form a composition comprising polylactide and lactide, and (c) removing said composition from the reactor, wherein the whole process is performed at pressures of at least 1 bar, and wherein the composition removed from the reactor is never subjected to a pressure below 1 bar.
The present invention also encompasses the use of a composition obtainable by the process according to the first aspect of the invention in applications where the composition degrades hydrolytically.
The present invention also encompasses the use of a composition obtainable by the present process in applications related to oil and gas production.
The present invention also encompasses the use of a composition obtainable by the present process as diverting agent.
FIELD OF THE INVENTION
The invention relates to a process for the preparation of a composition comprising polylactide and lactide.
BACKGROUND OF THE INVENTION
Polylactide, also referred as polylactic acid (PLA), is a synthetic aliphatic polyester derived from renewable resources, such a cane sugar, corn, sugar beet and cassava, which can furthermore be degraded under industrial composting conditions. There is currently a need in the industry to provide mixtures of lactide and PLA. This notably concerns applications where the articles require faster degradation kinetics than pure PLA with minimal amounts of lactide. In these applications up to tens of percents of lactide may be required.
Currently, the industry can prepare these mixtures by compounding PLA with lactide monomer in a given ratio and then shaping the final mixture. There is therefore a need to improve the processes of the prior art.
SUMMARY OF THE INVENTION
In a first aspect, the present invention concerns a process for the preparation of a composition comprising polylactide and lactide by ring-opening polymerization of lactide, said process comprising the steps of: (a) providing lactide and polymerization catalyst to a reactor, (b) melt polymerizing said lactide to a degree of polymerization of at most 96.0 %, to form a composition comprising polylactide and lactide, and (c) removing said composition from the reactor, wherein the whole process is performed at pressures of at least 1 bar, and wherein the composition removed from the reactor is never subjected to a pressure below 1 bar.
The present invention also encompasses the use of a composition obtainable by the process according to the first aspect of the invention in applications where the composition degrades hydrolytically.
The present invention also encompasses the use of a composition obtainable by the present process in applications related to oil and gas production.
The present invention also encompasses the use of a composition obtainable by the present process as diverting agent.
2 The present invention also encompasses the use of a composition obtainable by the present process as an acid release agent.
The present inventors have found that it is possible to produce directly from any PLA
polymerization plant such mixtures. The inventors have found that the desired lactide/PLA
composition may be produced by making sure that during the whole production process, the produced PLA/lactide mixture is not subjected to a pressure below 1 bar.
This process has significant benefits in terms of cost as a degassing step is avoided.
The above and other characteristics, features and advantages of the present invention will become apparent from the following detailed description, which illustrate, by way of example, the principles of the invention.
DETAILED DESCRIPTION OF THE INVENTION
When describing the invention, the terms used are to be construed in accordance with the following definitions, unless a context dictates otherwise.
Unless otherwise defined, all terms used in disclosing the invention, including technical and .. scientific terms, have the meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. By means of further guidance, term definitions are included to better appreciate the teaching of the present invention.
In the following passages, different aspects of the invention are defined in more detail. Each aspect so defined may be combined with any other aspect or aspects unless clearly indicated to the contrary. In particular, any feature indicated as being preferred or advantageous may be combined with any other feature or features indicated as being preferred or advantageous.
Reference throughout this specification to "one embodiment" or "an embodiment"
means that a particular feature, structure or characteristic described in connection with the embodiment is included in at least one embodiment of the present invention.
Thus, appearances of the phrases "in one embodiment" or "in an embodiment" in various places throughout this specification are not necessarily all referring to the same embodiment, but may. Furthermore, the particular features, structures or characteristics may be combined in any suitable manner, as would be apparent to a person skilled in the art from this disclosure, in one or more embodiments. Furthermore, while some embodiments described herein include some but not other features included in other embodiments, combinations of features of different embodiments are meant to be within the scope of the invention, and form different embodiments, as would be understood by those in the art.
The present inventors have found that it is possible to produce directly from any PLA
polymerization plant such mixtures. The inventors have found that the desired lactide/PLA
composition may be produced by making sure that during the whole production process, the produced PLA/lactide mixture is not subjected to a pressure below 1 bar.
This process has significant benefits in terms of cost as a degassing step is avoided.
The above and other characteristics, features and advantages of the present invention will become apparent from the following detailed description, which illustrate, by way of example, the principles of the invention.
DETAILED DESCRIPTION OF THE INVENTION
When describing the invention, the terms used are to be construed in accordance with the following definitions, unless a context dictates otherwise.
Unless otherwise defined, all terms used in disclosing the invention, including technical and .. scientific terms, have the meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. By means of further guidance, term definitions are included to better appreciate the teaching of the present invention.
In the following passages, different aspects of the invention are defined in more detail. Each aspect so defined may be combined with any other aspect or aspects unless clearly indicated to the contrary. In particular, any feature indicated as being preferred or advantageous may be combined with any other feature or features indicated as being preferred or advantageous.
Reference throughout this specification to "one embodiment" or "an embodiment"
means that a particular feature, structure or characteristic described in connection with the embodiment is included in at least one embodiment of the present invention.
Thus, appearances of the phrases "in one embodiment" or "in an embodiment" in various places throughout this specification are not necessarily all referring to the same embodiment, but may. Furthermore, the particular features, structures or characteristics may be combined in any suitable manner, as would be apparent to a person skilled in the art from this disclosure, in one or more embodiments. Furthermore, while some embodiments described herein include some but not other features included in other embodiments, combinations of features of different embodiments are meant to be within the scope of the invention, and form different embodiments, as would be understood by those in the art.
3 The terms "comprising", "comprises" and "comprised of" as used herein are synonymous with "including", "includes" or "containing", "contains", and are inclusive or open-ended and do not exclude additional, non-recited members, elements or method steps. It will be appreciated that the terms "comprising", "comprises" and "comprised of" as used herein .. comprise the terms "consisting of', "consists" and "consists of".
As used in the specification and the appended claims, the singular forms "a", "an," and "the"
include plural referents unless the context clearly dictates otherwise. By way of example, "a step" means one step or more than one step.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as is commonly understood by one of skill in the art. All publications referenced herein are incorporated by reference thereto.
The recitation of numerical ranges by endpoints includes all integer numbers and, where appropriate, fractions subsumed within that range (e.g. 1 to 5 can include 1, 2, 3, 4 when referring to, for example, a number of elements, and can also include 1.5, 2, 2.75 and 3.80, when referring to, for example, measurements). The recitation of end points also includes the end point values themselves (e.g. from 1.0 to 5.0 includes both 1.0 and 5.0). Any numerical range recited herein is intended to include all sub-ranges subsumed therein.
Whenever the term "substituted" is used in the present invention, it is meant to indicate that one or more hydrogens on the atom indicated in the expression using "substituted" is replaced with a selection from the indicated group, provided that the indicated atom's normal valency is not exceeded, and that the substitution results in a chemically stable compound. Where groups can be substituted, such groups may be substituted with one or more, and preferably one, two or three substituents.
The term "alkyl", as a group or part of a group, refers to a hydrocarbyl group of formula CnH2n+1 wherein n is a number of at least 1. Alkyl groups may be linear, or branched and may be substituted as indicated herein. Generally, the alkyl groups comprise from 1 to 20 carbon atoms, preferably from 1 to 12 carbon atoms, preferably from 1 to 10 carbon atoms, preferably from 1 to 8 carbon atoms, preferably from 1 to 6 carbon atoms, more preferably 1, 2, 3, 4, 5, 6 carbon atoms. When a subscript is used herein following a carbon atom, the subscript refers to the number of carbon atoms that the named group may contain. For example, the term "C1_20alkyl", as a group or part of a group, refers to a hydrocarbyl group of Formula CnH2n+1 wherein n is a number ranging from 1 to 20. Thus, for example, C1_20alkyl groups include all linear, or branched alkyl groups having 1 to 20 carbon atoms, and thus includes for example methyl, ethyl, n-propyl, i-propyl, 2-methyl-ethyl, butyl and its isomers
As used in the specification and the appended claims, the singular forms "a", "an," and "the"
include plural referents unless the context clearly dictates otherwise. By way of example, "a step" means one step or more than one step.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as is commonly understood by one of skill in the art. All publications referenced herein are incorporated by reference thereto.
The recitation of numerical ranges by endpoints includes all integer numbers and, where appropriate, fractions subsumed within that range (e.g. 1 to 5 can include 1, 2, 3, 4 when referring to, for example, a number of elements, and can also include 1.5, 2, 2.75 and 3.80, when referring to, for example, measurements). The recitation of end points also includes the end point values themselves (e.g. from 1.0 to 5.0 includes both 1.0 and 5.0). Any numerical range recited herein is intended to include all sub-ranges subsumed therein.
Whenever the term "substituted" is used in the present invention, it is meant to indicate that one or more hydrogens on the atom indicated in the expression using "substituted" is replaced with a selection from the indicated group, provided that the indicated atom's normal valency is not exceeded, and that the substitution results in a chemically stable compound. Where groups can be substituted, such groups may be substituted with one or more, and preferably one, two or three substituents.
The term "alkyl", as a group or part of a group, refers to a hydrocarbyl group of formula CnH2n+1 wherein n is a number of at least 1. Alkyl groups may be linear, or branched and may be substituted as indicated herein. Generally, the alkyl groups comprise from 1 to 20 carbon atoms, preferably from 1 to 12 carbon atoms, preferably from 1 to 10 carbon atoms, preferably from 1 to 8 carbon atoms, preferably from 1 to 6 carbon atoms, more preferably 1, 2, 3, 4, 5, 6 carbon atoms. When a subscript is used herein following a carbon atom, the subscript refers to the number of carbon atoms that the named group may contain. For example, the term "C1_20alkyl", as a group or part of a group, refers to a hydrocarbyl group of Formula CnH2n+1 wherein n is a number ranging from 1 to 20. Thus, for example, C1_20alkyl groups include all linear, or branched alkyl groups having 1 to 20 carbon atoms, and thus includes for example methyl, ethyl, n-propyl, i-propyl, 2-methyl-ethyl, butyl and its isomers
4 (e.g. n-butyl, i-butyl and t-butyl); pentyl and its isomers, hexyl and its isomers, heptyl and its isomers, octyl and its isomers, nonyl and its isomers, decyl and its isomers, undecyl and its isomers, dodecyl and its isomers, tridecyl and its isomers, tetradecyl and its isomers, pentadecyl and its isomers, hexadecyl and its isomers, heptadecyl and its isomers, octadecyl and its isomers, nonadecyl and its isomers, icosyl and its isomers, and the like. .
For example, Ci_ioalkyl includes all linear, or branched alkyl groups having 1 to 10 carbon atoms, and thus includes for example methyl, ethyl, n-propyl, i-propyl, 2-methyl-ethyl, butyl and its isomers (e.g. n-butyl, i-butyl and t-butyl); pentyl and its isomers, hexyl and its isomers, heptyl and its isomers, octyl and its isomers, nonyl and its isomers, decyl and its isomers and the like. Thus, for example, Ci_salkyl groups include all linear, or branched alkyl groups having 1 to 8 carbon atoms, and thus includes for example methyl, ethyl, n-propyl, i-propyl, 2-methyl-ethyl, butyl and its isomers (e.g. n-butyl, i-butyl and t-butyl);
pentyl and its isomers, hexyl and its isomers, heptyl and its isomers, octyl and its isomers, and the like. For example, Ci_salkyl includes all linear or branched alkyl groups having 1 to 6 carbon atoms, and thus includes for example methyl, ethyl, n-propyl, i-propyl, 2-methyl-ethyl, butyl and its isomers (e.g. n-butyl, i-butyl and t-butyl); pentyl and its isomers, hexyl and its isomers, and the like.
For example, Ci_aalkyl includes all linear or branched alkyl groups having 1 to 4 carbon atoms, and thus includes for example methyl, ethyl, n-propyl, i-propyl, 2-methyl-ethyl, butyl and its isomers (e.g. n-butyl, i-butyl and t-butyl), and the like. When the suffix "ene" is used in conjunction with an alkyl group, i.e. "alkylene", this is intended to mean the alkyl group as defined herein having two single bonds as points of attachment to other groups.
The term "C6_30aryl", as a group or part of a group, refers to a polyunsaturated, aromatic hydrocarbyl group having a single ring (i.e. phenyl) or multiple aromatic rings fused together (e.g. naphthalene), or linked covalently, typically containing 6 to 30 atoms;
wherein at least one ring is aromatic. The aromatic ring may optionally include one to two additional rings (either cycloalkyl, heterocyclyl or heteroaryl)fused thereto. Examples of suitable aryl include Cs_ioaryl, more preferably C6_8aryl. Non-limiting examples of C6_30aryl comprise phenyl, biphenylyl, biphenylenyl, or 1-or 2-naphthanely1; 5- or 6-tetralinyl, 1-, 2-, 3-, 4-, 5-, 6-, 7- or 8-azulenyl, 4-, 5-, 6 or 7-indenyl, 4- or 5-indanyl, 5-, 6-, 7- or 8-tetrahydronaphthyl, 1,2,3,4-tetrahydronaphthyl, and 1,4-dihydronaphthyl. When the suffix "ene" is used in conjunction with an aryl group, this is intended to mean the aryl group as defined herein having two single bonds as points of attachment to other groups. Suitable arylene groups include 1,4-phenylene, 1,2-phenylene, 1,3-phenylene, biphenylylene, naphthylene, indenylene, and the like.
The term "C6_30arylC1_20alkyl", as a group or part of a group, means a Ci_20alkyl as defined herein, wherein at least one hydrogen atom is replaced by at least one C6_30aryl as defined herein. Non-limiting examples of C6_30arylC1_20alkyl group include benzyl, phenethyl, dibenzylmethyl, methylphenylmethyl, 3-(2-naphthyl)-butyl, and the like.
For example, Ci_ioalkyl includes all linear, or branched alkyl groups having 1 to 10 carbon atoms, and thus includes for example methyl, ethyl, n-propyl, i-propyl, 2-methyl-ethyl, butyl and its isomers (e.g. n-butyl, i-butyl and t-butyl); pentyl and its isomers, hexyl and its isomers, heptyl and its isomers, octyl and its isomers, nonyl and its isomers, decyl and its isomers and the like. Thus, for example, Ci_salkyl groups include all linear, or branched alkyl groups having 1 to 8 carbon atoms, and thus includes for example methyl, ethyl, n-propyl, i-propyl, 2-methyl-ethyl, butyl and its isomers (e.g. n-butyl, i-butyl and t-butyl);
pentyl and its isomers, hexyl and its isomers, heptyl and its isomers, octyl and its isomers, and the like. For example, Ci_salkyl includes all linear or branched alkyl groups having 1 to 6 carbon atoms, and thus includes for example methyl, ethyl, n-propyl, i-propyl, 2-methyl-ethyl, butyl and its isomers (e.g. n-butyl, i-butyl and t-butyl); pentyl and its isomers, hexyl and its isomers, and the like.
For example, Ci_aalkyl includes all linear or branched alkyl groups having 1 to 4 carbon atoms, and thus includes for example methyl, ethyl, n-propyl, i-propyl, 2-methyl-ethyl, butyl and its isomers (e.g. n-butyl, i-butyl and t-butyl), and the like. When the suffix "ene" is used in conjunction with an alkyl group, i.e. "alkylene", this is intended to mean the alkyl group as defined herein having two single bonds as points of attachment to other groups.
The term "C6_30aryl", as a group or part of a group, refers to a polyunsaturated, aromatic hydrocarbyl group having a single ring (i.e. phenyl) or multiple aromatic rings fused together (e.g. naphthalene), or linked covalently, typically containing 6 to 30 atoms;
wherein at least one ring is aromatic. The aromatic ring may optionally include one to two additional rings (either cycloalkyl, heterocyclyl or heteroaryl)fused thereto. Examples of suitable aryl include Cs_ioaryl, more preferably C6_8aryl. Non-limiting examples of C6_30aryl comprise phenyl, biphenylyl, biphenylenyl, or 1-or 2-naphthanely1; 5- or 6-tetralinyl, 1-, 2-, 3-, 4-, 5-, 6-, 7- or 8-azulenyl, 4-, 5-, 6 or 7-indenyl, 4- or 5-indanyl, 5-, 6-, 7- or 8-tetrahydronaphthyl, 1,2,3,4-tetrahydronaphthyl, and 1,4-dihydronaphthyl. When the suffix "ene" is used in conjunction with an aryl group, this is intended to mean the aryl group as defined herein having two single bonds as points of attachment to other groups. Suitable arylene groups include 1,4-phenylene, 1,2-phenylene, 1,3-phenylene, biphenylylene, naphthylene, indenylene, and the like.
The term "C6_30arylC1_20alkyl", as a group or part of a group, means a Ci_20alkyl as defined herein, wherein at least one hydrogen atom is replaced by at least one C6_30aryl as defined herein. Non-limiting examples of C6_30arylC1_20alkyl group include benzyl, phenethyl, dibenzylmethyl, methylphenylmethyl, 3-(2-naphthyl)-butyl, and the like.
5 The term "hydroxyl" or "hydroxy" as used herein refers to the group -OH.
The terms described above and others used in the specification are well understood to those in the art.
Preferred statements, features, and embodiments of the processes of this invention are now set forth. Each statements and embodiments of the invention so defined may be combined with any other statement and/or embodiments unless clearly indicated to the contrary. In particular, any feature indicated as being preferred or advantageous may be combined with any other feature or features indicated as being preferred or advantageous.
In accordance with the present invention, a process is provided for the preparation of a composition comprising polylactide and lactide. Said process is performed by ring-opening .. polymerization of lactide. The process of the invention comprises the steps of: providing lactide and a polymerization catalyst to a reactor, melt polymerizing said lactide to a degree of polymerization (also synonymously referred as "degree of conversion" or "conversion") of at most 96.0 %, for example at most 95.0 %, for example at most 90.0 %, to form a composition comprising polylactide and lactide, and removing said composition from the reactor, wherein the whole process is performed at pressures of at least 1 bar, and wherein the composition removed from the reactor is never subjected to pressures below 1 bar.
Preferably, the prepared composition comprises at least 4.0 % by weight of lactide, preferably at least 5.0 % by weight, preferably at least 10.0 % by weight, based on the total weight of the composition.
.. Preferably, the process of the invention comprises the steps of: providing lactide and polymerization catalyst to a reactor, melt polymerizing said lactide to a degree of conversion of at most 96.0 %, for example at most 95.0 %, for example at most 90.0 %, to form a composition comprising polylactide and lactide, and removing said composition from the reactor, wherein the whole process is performed at pressures of at least 1 bar, and wherein the composition removed from the reactor is not subjected to one or more devolatilization steps, wherein preferably, the obtained and dried composition comprises at least 4.0 % by weight of lactide, preferably at least 5.0 % by weight, preferably at least 10.0 % by weight of lactide, based on the total weight of the composition.
The terms described above and others used in the specification are well understood to those in the art.
Preferred statements, features, and embodiments of the processes of this invention are now set forth. Each statements and embodiments of the invention so defined may be combined with any other statement and/or embodiments unless clearly indicated to the contrary. In particular, any feature indicated as being preferred or advantageous may be combined with any other feature or features indicated as being preferred or advantageous.
In accordance with the present invention, a process is provided for the preparation of a composition comprising polylactide and lactide. Said process is performed by ring-opening .. polymerization of lactide. The process of the invention comprises the steps of: providing lactide and a polymerization catalyst to a reactor, melt polymerizing said lactide to a degree of polymerization (also synonymously referred as "degree of conversion" or "conversion") of at most 96.0 %, for example at most 95.0 %, for example at most 90.0 %, to form a composition comprising polylactide and lactide, and removing said composition from the reactor, wherein the whole process is performed at pressures of at least 1 bar, and wherein the composition removed from the reactor is never subjected to pressures below 1 bar.
Preferably, the prepared composition comprises at least 4.0 % by weight of lactide, preferably at least 5.0 % by weight, preferably at least 10.0 % by weight, based on the total weight of the composition.
.. Preferably, the process of the invention comprises the steps of: providing lactide and polymerization catalyst to a reactor, melt polymerizing said lactide to a degree of conversion of at most 96.0 %, for example at most 95.0 %, for example at most 90.0 %, to form a composition comprising polylactide and lactide, and removing said composition from the reactor, wherein the whole process is performed at pressures of at least 1 bar, and wherein the composition removed from the reactor is not subjected to one or more devolatilization steps, wherein preferably, the obtained and dried composition comprises at least 4.0 % by weight of lactide, preferably at least 5.0 % by weight, preferably at least 10.0 % by weight of lactide, based on the total weight of the composition.
6 More preferably, the process of the invention comprises the steps of:
providing lactide and polymerization catalyst to a reactor, melt polymerizing said lactide to a degree of polymerization of below 96.0 %, to form a composition comprising polylactide and lactide, and removing said composition from the reactor, wherein the whole process is performed at pressures of at least 1 bar, and wherein the composition removed from the reactor is not subjected to one or more devolatilization steps, at a pressure below 1 bar.
The present invention pertains to the preparation of a composition using polymerization carried out in the substantial absence of solvent, namely to melt-polymerization. If so desired minor amounts of solvent may be present in the process, e.g. added as a solvent for the catalyst or further reaction components. The process is intended to encompass situations where the reaction mixture contains less than 5 % by weight of solvent, in particular less than 2 % by weight, more in particular less than 1 % by weight, still more in particular less than 0.5 % by weight of solvent.
The polymerization process can be batch melt process or a continuous melt process.
The polymerization is preferably performed in inert conditions, such as under a dry nitrogen or argon blanket.
The ring-opening polymerization can be performed at a temperature of at least 100 C. For example the polymerization can be performed at a temperature ranging from 100 C-240 C, preferably from 100 C-220 C, yet more preferably from 100 C-200 C.
In some preferred embodiments, the process is a continuous melt process, and comprises the steps of a) continuously providing lactide and polymerization catalyst and optionally a co-initiator, to a first polymerization reactor for a polymerization, b) continuously removing polymerized reaction mixture from the first polymerization reactor and continuously providing polymerized reaction mixture to a second polymerization reactor, wherein the reaction mixture is further polymerized to a degree of polymerization of at most 96.0 % to form the composition, and c) continuously removing the composition from the polymerization reactor.
Both the polymerization in the first polymerization reactor and the polymerization in the second polymerization reactor can be performed in inert conditions, such as under a dry nitrogen or argon blanket.
The ring-opening polymerization in the first polymerization reactor and the polymerization in the second polymerization reactor can be performed at a temperature of at least 100 C, preferably at a temperature ranging from 100 C-240 C, preferably from 100 C-220 C, yet
providing lactide and polymerization catalyst to a reactor, melt polymerizing said lactide to a degree of polymerization of below 96.0 %, to form a composition comprising polylactide and lactide, and removing said composition from the reactor, wherein the whole process is performed at pressures of at least 1 bar, and wherein the composition removed from the reactor is not subjected to one or more devolatilization steps, at a pressure below 1 bar.
The present invention pertains to the preparation of a composition using polymerization carried out in the substantial absence of solvent, namely to melt-polymerization. If so desired minor amounts of solvent may be present in the process, e.g. added as a solvent for the catalyst or further reaction components. The process is intended to encompass situations where the reaction mixture contains less than 5 % by weight of solvent, in particular less than 2 % by weight, more in particular less than 1 % by weight, still more in particular less than 0.5 % by weight of solvent.
The polymerization process can be batch melt process or a continuous melt process.
The polymerization is preferably performed in inert conditions, such as under a dry nitrogen or argon blanket.
The ring-opening polymerization can be performed at a temperature of at least 100 C. For example the polymerization can be performed at a temperature ranging from 100 C-240 C, preferably from 100 C-220 C, yet more preferably from 100 C-200 C.
In some preferred embodiments, the process is a continuous melt process, and comprises the steps of a) continuously providing lactide and polymerization catalyst and optionally a co-initiator, to a first polymerization reactor for a polymerization, b) continuously removing polymerized reaction mixture from the first polymerization reactor and continuously providing polymerized reaction mixture to a second polymerization reactor, wherein the reaction mixture is further polymerized to a degree of polymerization of at most 96.0 % to form the composition, and c) continuously removing the composition from the polymerization reactor.
Both the polymerization in the first polymerization reactor and the polymerization in the second polymerization reactor can be performed in inert conditions, such as under a dry nitrogen or argon blanket.
The ring-opening polymerization in the first polymerization reactor and the polymerization in the second polymerization reactor can be performed at a temperature of at least 100 C, preferably at a temperature ranging from 100 C-240 C, preferably from 100 C-220 C, yet
7 more preferably from 100 C-200 C. The temperature in both polymerization reactors may be the same or different.
In some embodiment, when a first polymerization is used, lactide and polymerization catalyst can be continuously provided to a continuous mixing reactor, as first polymerization reactor. Suitable continuous mixing reactors include continuously stirred tank reactors and loop reactors, both of which are known in the art. Polymerization in a loop reactor can be preferred. In some embodiments, the first polymerization reactor can comprises static mixing elements.
The degree of polymerization in the first reactor can be generally at least 5 % by weight, more in particular at least 10 % by weight. The degree of polymerization may be as high as 50 % by weight, or even as high as 60 % by weight.
The second polymerization reactor can be also equipped with static mixing elements. In one embodiment, the first polymerization and/or the second polymerization reactor are static mixer reactors. That is, reactors equipped with static mixing elements.
Suitable static mixing elements are known in the art, examples thereof are described in US
4,314,606.
The second polymerization reactor can be a plug flow reactor. The first polymerized reaction mixture can be continuously withdrawn from the first polymerization reactor and continuously provided to a plug flow reactor, where it is polymerized further to a degree of polymerization of at most 96.0 %. The plug flow reactor can be equipped with static mixing elements. The plug flow reactor can be placed vertically or tilted.
In some preferred embodiments, the process is a continuous melt process, and comprises the steps of a) continuously providing lactide and polymerization catalyst to a continuous mixing reactor for a first polymerization, b) continuously removing first polymerized reaction mixture from the continuous mixing reactor and continuously providing first polymerized reaction mixture to a plug flow reactor, wherein the reaction mixture is polymerized to a degree of polymerization of at most 96.0 % to form the composition, and c) continuously removing the composition from the plug flow reactor.
The main reactants provided to the reactor include lactide and polymerization catalyst. If so desired, additional components such as co-catalyst, initiator for molecular weight control and/or additives may also be added. The components can be added to the reactor directly, either pure or in a solvent, or (some of) the reactants may be combined prior to addition to the reactor. The point of addition of the additives will depend on the function of the additive;
In some embodiment, when a first polymerization is used, lactide and polymerization catalyst can be continuously provided to a continuous mixing reactor, as first polymerization reactor. Suitable continuous mixing reactors include continuously stirred tank reactors and loop reactors, both of which are known in the art. Polymerization in a loop reactor can be preferred. In some embodiments, the first polymerization reactor can comprises static mixing elements.
The degree of polymerization in the first reactor can be generally at least 5 % by weight, more in particular at least 10 % by weight. The degree of polymerization may be as high as 50 % by weight, or even as high as 60 % by weight.
The second polymerization reactor can be also equipped with static mixing elements. In one embodiment, the first polymerization and/or the second polymerization reactor are static mixer reactors. That is, reactors equipped with static mixing elements.
Suitable static mixing elements are known in the art, examples thereof are described in US
4,314,606.
The second polymerization reactor can be a plug flow reactor. The first polymerized reaction mixture can be continuously withdrawn from the first polymerization reactor and continuously provided to a plug flow reactor, where it is polymerized further to a degree of polymerization of at most 96.0 %. The plug flow reactor can be equipped with static mixing elements. The plug flow reactor can be placed vertically or tilted.
In some preferred embodiments, the process is a continuous melt process, and comprises the steps of a) continuously providing lactide and polymerization catalyst to a continuous mixing reactor for a first polymerization, b) continuously removing first polymerized reaction mixture from the continuous mixing reactor and continuously providing first polymerized reaction mixture to a plug flow reactor, wherein the reaction mixture is polymerized to a degree of polymerization of at most 96.0 % to form the composition, and c) continuously removing the composition from the plug flow reactor.
The main reactants provided to the reactor include lactide and polymerization catalyst. If so desired, additional components such as co-catalyst, initiator for molecular weight control and/or additives may also be added. The components can be added to the reactor directly, either pure or in a solvent, or (some of) the reactants may be combined prior to addition to the reactor. The point of addition of the additives will depend on the function of the additive;
8 PCT/EP2019/066883 antioxidants may for example be added prior to the first polymerization, whereas catalyst deactivators are generally added after the polymerization is completed.
Lactide for use in the process includes L-lactide, which is a cyclic dimer of L-lactic acid; D-lactide, which is a cyclic dimer of D-lactic acid; meso-lactide, which is a cyclic dimer of D-lactic acid and L-lactic acid; and DL-lactide, which is a racemate of D-lactide and L-lactide.
Mixtures of the aforementioned lactides are also suitable for use in the process.
Random copolymers made from meso-lactide generally result in an atactic primary structure referred to as poly(meso-lactide) (PmesoLA) and are amorphous. Random optical copolymers made from equimolar amounts of D-lactide and L-lactide are referred to as poly(rac-lactide) and are also amorphous, unless stereoselective catalyst are employed upon which a wealth of structures are possible with varying thermal properties. The term "L-lactide" or "L-L-lactide" refers to (S,S)-lactide and is the cyclic di-ester of two lactic acid S
enantiomers. The term "D-lactide" or "D-D-lactide" refers to (R,R)-lactide and is a cyclic di-ester of two lactic acid R enantiomers.
The polymerization catalyst employed for this process may have general formula m(y1,y2, ...YP)q, in which M is a metal selected from the group comprising the elements of columns 3 to 12 of the periodic table of the elements, as well as the elements Al, Ga, In, TI, Ge, Sn, Pb, Sb, Ca, Mg and Bi; whereas Y1, Y2, ... YP are each substituents selected from the group comprising alkyl with 1 to 20 carbon atoms, aryl having from 6 to 30 carbon atoms, alkoxy having from 1 to 20 carbon atoms, aryloxy having from 6 to 30 carbon atoms, and other oxide, carboxylate, and halide groups as well as elements of group 15 and/or 16 of the periodic table; p and q are integers of from 1 to 6. As examples of suitable catalysts, we may notably mention the catalysts of Sn, Ti, Zr, Zn, and Bi; preferably an alkoxide or a carboxylate and more preferably Sn(Oct)2, Ti(OiPr)4, Ti(2-ethylhexanoate)4, Ti(2-ethylhexyloxide)4, Zr(OiPr)4, Zirkonium tris(phenolates) as mentioned in W02014177543, (2 ,4-d i-tert-butyl-6-(((2-(d imethylami no) ethyl)(methyl)amino)methyl)phenoxy) (ethoxy)zinc, or Zn(lactate)2.
The catalyst concentration can be generally at least 5 ppm, calculated as metal weight, more in particular at least 10 ppm, for example at least 30 ppm, for example at least 40 ppm.
The catalyst concentration can be generally at most 300 ppm, in particular at most 150 ppm.
If so desired, co-catalyst may be added to the lactide and the catalyst, that is, a compound that further increases the polymerization rate. Suitable co-catalysts are known in the art.
Reference is made, for example, to US 6,166,169.
Lactide for use in the process includes L-lactide, which is a cyclic dimer of L-lactic acid; D-lactide, which is a cyclic dimer of D-lactic acid; meso-lactide, which is a cyclic dimer of D-lactic acid and L-lactic acid; and DL-lactide, which is a racemate of D-lactide and L-lactide.
Mixtures of the aforementioned lactides are also suitable for use in the process.
Random copolymers made from meso-lactide generally result in an atactic primary structure referred to as poly(meso-lactide) (PmesoLA) and are amorphous. Random optical copolymers made from equimolar amounts of D-lactide and L-lactide are referred to as poly(rac-lactide) and are also amorphous, unless stereoselective catalyst are employed upon which a wealth of structures are possible with varying thermal properties. The term "L-lactide" or "L-L-lactide" refers to (S,S)-lactide and is the cyclic di-ester of two lactic acid S
enantiomers. The term "D-lactide" or "D-D-lactide" refers to (R,R)-lactide and is a cyclic di-ester of two lactic acid R enantiomers.
The polymerization catalyst employed for this process may have general formula m(y1,y2, ...YP)q, in which M is a metal selected from the group comprising the elements of columns 3 to 12 of the periodic table of the elements, as well as the elements Al, Ga, In, TI, Ge, Sn, Pb, Sb, Ca, Mg and Bi; whereas Y1, Y2, ... YP are each substituents selected from the group comprising alkyl with 1 to 20 carbon atoms, aryl having from 6 to 30 carbon atoms, alkoxy having from 1 to 20 carbon atoms, aryloxy having from 6 to 30 carbon atoms, and other oxide, carboxylate, and halide groups as well as elements of group 15 and/or 16 of the periodic table; p and q are integers of from 1 to 6. As examples of suitable catalysts, we may notably mention the catalysts of Sn, Ti, Zr, Zn, and Bi; preferably an alkoxide or a carboxylate and more preferably Sn(Oct)2, Ti(OiPr)4, Ti(2-ethylhexanoate)4, Ti(2-ethylhexyloxide)4, Zr(OiPr)4, Zirkonium tris(phenolates) as mentioned in W02014177543, (2 ,4-d i-tert-butyl-6-(((2-(d imethylami no) ethyl)(methyl)amino)methyl)phenoxy) (ethoxy)zinc, or Zn(lactate)2.
The catalyst concentration can be generally at least 5 ppm, calculated as metal weight, more in particular at least 10 ppm, for example at least 30 ppm, for example at least 40 ppm.
The catalyst concentration can be generally at most 300 ppm, in particular at most 150 ppm.
If so desired, co-catalyst may be added to the lactide and the catalyst, that is, a compound that further increases the polymerization rate. Suitable co-catalysts are known in the art.
Reference is made, for example, to US 6,166,169.
9 The process can be performed in the presence of a co-initiator of formula R1-0H, wherein R1 is selected from the group consisting of C1_20alkyl, C6_30aryl, and C6_30arylC1_20alkyl optionally substituted by one or more substituents selected from the group consisting of halogen, hydroxyl, and Ci_salkyl. Preferably, R1 is selected from C3_12alkyl, Cs_ioaryl, and Cs_ioarylCi_ualkyl, optionally substituted by one or more substituents, each independently selected from the group consisting of halogen, hydroxyl, and Ci_salkyl;
preferably, R1 is selected from C3_12alkyl, Cs_ioaryl, and Cs_ioarylCi_ualkyl, optionally substituted by one or more substituents, each independently selected from the group consisting of halogen, hydroxyl and Ci_aalkyl. The initiator can be an alcohol. The alcohol can be a polyol such as diol, triol or higher functionality polyhydric alcohol. The alcohol may be derived from biomass such as for instance glycerol or propanediol or any other sugar-based alcohol such as for example erythritol. The alcohol can be used alone or in combination with another alcohol. In an embodiment, non-limiting examples of initiators include 1-octanol, 1-decanol, isopropanol, propanediol, trimethylolpropane, 2-butanol, 3-buten-2-ol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, 1,7-heptanediol, benzyl alcohol, 4-bromopheno1,1,4-benzenedimethanol, and (4-trifluoromethyl)benzyl alcohol; preferably, said compound is selected from 1-octanol, isopropanol, and 1,4-butanediol.
Selection of an appropriate co-catalyst, initiator and optional additives such as anti-oxidants, phosphates, epoxidised vegetable oil, plasticisers, catkillers, etcetera, is within the scope of the person skilled in the art.
In step b) of the process the polymerization reaction is carried out further until a conversion of at most 96.0 % is obtained, calculated on the starting lactide. Conversion is to be determined directly after polymerization or real-time by online techniques such as mid-IR, near-IR and Raman spectroscopy.
Preferably, the prepared composition comprises at least 4.0 % by weight of lactide, preferably at least 5.0 % by weight, preferably at least 10.0 % by weight, based on the total weight of the composition. For higher lactide concentrations, polymerization settings can be adjusted to decrease the conversion rate of the lactide polymerization process. Settings may include polymerization temperature, catalyst and initiator concentration and process throughput. For example, the catalyst deactivator dosing point can be positioned further down-stream in the process.
The composition may be subjected to a stabilization step. Stabilization step comprises treatment of the composition as obtained from the reactor with compounds that increase the stability of the compound against further polymerization, depolymerization, discoloring and degradation in general. Examples of suitable compounds for stabilization are organic peroxides, anti-oxidants such as phosphite-containing compounds, multi-functional carboxylic acids, hindered phenolic compounds, catalyst deactivating agents such as hindered alkyl, aryl and phenolic hydrazides, amides of aliphatic and aromatic mono- and 5 dicarboxylic acids, cyclic amides, hydrazones and bishydrazones of aliphatic and aromatic aldehydes, hydrazides of aliphatic and aromatic mono- and dicarboxylic acids, bis-acylated hydrazine derivatives, heterocyclic compounds, endcapping with anhydrides, and mixtures thereof. The polymer is treated with the stabilization compounds by admixing the stabilizing compound with the composition, e.g., at a temperature of the same order as the
preferably, R1 is selected from C3_12alkyl, Cs_ioaryl, and Cs_ioarylCi_ualkyl, optionally substituted by one or more substituents, each independently selected from the group consisting of halogen, hydroxyl and Ci_aalkyl. The initiator can be an alcohol. The alcohol can be a polyol such as diol, triol or higher functionality polyhydric alcohol. The alcohol may be derived from biomass such as for instance glycerol or propanediol or any other sugar-based alcohol such as for example erythritol. The alcohol can be used alone or in combination with another alcohol. In an embodiment, non-limiting examples of initiators include 1-octanol, 1-decanol, isopropanol, propanediol, trimethylolpropane, 2-butanol, 3-buten-2-ol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, 1,7-heptanediol, benzyl alcohol, 4-bromopheno1,1,4-benzenedimethanol, and (4-trifluoromethyl)benzyl alcohol; preferably, said compound is selected from 1-octanol, isopropanol, and 1,4-butanediol.
Selection of an appropriate co-catalyst, initiator and optional additives such as anti-oxidants, phosphates, epoxidised vegetable oil, plasticisers, catkillers, etcetera, is within the scope of the person skilled in the art.
In step b) of the process the polymerization reaction is carried out further until a conversion of at most 96.0 % is obtained, calculated on the starting lactide. Conversion is to be determined directly after polymerization or real-time by online techniques such as mid-IR, near-IR and Raman spectroscopy.
Preferably, the prepared composition comprises at least 4.0 % by weight of lactide, preferably at least 5.0 % by weight, preferably at least 10.0 % by weight, based on the total weight of the composition. For higher lactide concentrations, polymerization settings can be adjusted to decrease the conversion rate of the lactide polymerization process. Settings may include polymerization temperature, catalyst and initiator concentration and process throughput. For example, the catalyst deactivator dosing point can be positioned further down-stream in the process.
The composition may be subjected to a stabilization step. Stabilization step comprises treatment of the composition as obtained from the reactor with compounds that increase the stability of the compound against further polymerization, depolymerization, discoloring and degradation in general. Examples of suitable compounds for stabilization are organic peroxides, anti-oxidants such as phosphite-containing compounds, multi-functional carboxylic acids, hindered phenolic compounds, catalyst deactivating agents such as hindered alkyl, aryl and phenolic hydrazides, amides of aliphatic and aromatic mono- and 5 dicarboxylic acids, cyclic amides, hydrazones and bishydrazones of aliphatic and aromatic aldehydes, hydrazides of aliphatic and aromatic mono- and dicarboxylic acids, bis-acylated hydrazine derivatives, heterocyclic compounds, endcapping with anhydrides, and mixtures thereof. The polymer is treated with the stabilization compounds by admixing the stabilizing compound with the composition, e.g., at a temperature of the same order as the
10 polymerization temperature. This can be done by means of a static mixer, an extruder, or any other conventional way of mixing materials of which at least one is highly viscous. In some preferred embodiments, the polymerization is stopped by addition of one or more catalyst deactivator.
The composition formed is then removed from the polymerization reactor.
According to a preferred embodiment of the invention, the composition obtained is not subjected to a devolatilization step, and if residence time in devolatilizers is used they are used at a pressure of at least 1 bar. The composition is therefore not subjected to a pressure below 1 bar.
Examples of devolatilizers include extruders, especially twin screw extruders, wiped film evaporators, falling film evaporators, rotary devolatilizers, rotary disk devolatilizers, centrifugal devolatilizers, flat plate devolatilizers, and static expansion chambers, such as those involving special distributors, e.g., Sulzer devolatilization technology as described in EP1800724.
The composition can be dried. Optionally, a crystallization step may be performed before the drying step. Due to the high levels of lactide in the final composition, care has to be taken that no lactide sublimation occurs at undesired locations. To avoid occurrence of such phenomena a number of steps can be taken including prevention of cold spots, use of low crystallization and drying temperatures as well as high pressures (>1 bar) during optional crystallization and drying.
The composition can then be directly further processed to end-use by extrusion, blow-molding, film casting, film blowing, thermoforming, foaming, or fiber-spinning at elevated temperatures to form useful articles. If so desired, the polymer may be compounded with additives such as anti-oxidants, nucleating agents, mineral fillers, glass or natural fibers, processing aids, UV-stabilizers, or other polymer-additives known to the skilled person.
The composition formed is then removed from the polymerization reactor.
According to a preferred embodiment of the invention, the composition obtained is not subjected to a devolatilization step, and if residence time in devolatilizers is used they are used at a pressure of at least 1 bar. The composition is therefore not subjected to a pressure below 1 bar.
Examples of devolatilizers include extruders, especially twin screw extruders, wiped film evaporators, falling film evaporators, rotary devolatilizers, rotary disk devolatilizers, centrifugal devolatilizers, flat plate devolatilizers, and static expansion chambers, such as those involving special distributors, e.g., Sulzer devolatilization technology as described in EP1800724.
The composition can be dried. Optionally, a crystallization step may be performed before the drying step. Due to the high levels of lactide in the final composition, care has to be taken that no lactide sublimation occurs at undesired locations. To avoid occurrence of such phenomena a number of steps can be taken including prevention of cold spots, use of low crystallization and drying temperatures as well as high pressures (>1 bar) during optional crystallization and drying.
The composition can then be directly further processed to end-use by extrusion, blow-molding, film casting, film blowing, thermoforming, foaming, or fiber-spinning at elevated temperatures to form useful articles. If so desired, the polymer may be compounded with additives such as anti-oxidants, nucleating agents, mineral fillers, glass or natural fibers, processing aids, UV-stabilizers, or other polymer-additives known to the skilled person.
11 It is also possible to process the composition into particles such as beads, chips, or other pelletized or powdered products in manners known in the art and then sold to end-users.
The composition preferably comprises polylactide and at least 4.0 % by weight of lactide, for example at least 5.0 % by weight of lactide, for example at least 10.0 %
by weight of lactide. The absolute weight average molecular weight (Mw) of the polylactide in the final composition can be generally at least 10 kg/mol, for example at least 40 kg/mol, for example ranging from 40 to 550 kg/mol, for example from 50 to 350 kg/mol, for example from 50 to 300 kg/mol, and for example from 50 to 200 kg/mol.
The present inventors have shown that a composition comprising lactide and PLA
can be prepared using a melt processes, wherein the typical PLA degassing step can be omitted and the wherein polymerization does not have to be driven to thermodynamic equilibrium.
The present process for preparing lactide and PLA mixture prevents having to mix lactide and PLA via additional extrusion.
Compositions obtainable/obtained by the present process are particularly useful in applications where the composition degrades hydrolytically.
Compositions obtainable/obtained by the present process are also particularly useful in applications related to oil and gas production.
The compositions obtainable/obtained by the present process may be used as diverting agent.
The compositions obtainable/obtained by the present process may also be used as an acid release agent.
The present invention can be further illustrated by the following examples, although it will be understood that these examples are included merely for purposes of illustration and are not intended to limit the scope of the invention unless otherwise specifically indicated.
EXAMPLES
Unless otherwise indicated, all parts and all percentages in the following examples, as well as throughout the specification, are parts by weight or percentages by weight respectively.
Methods Inherent viscosities of the different samples were determined by the following method, compliant with DIN 51562.
The composition preferably comprises polylactide and at least 4.0 % by weight of lactide, for example at least 5.0 % by weight of lactide, for example at least 10.0 %
by weight of lactide. The absolute weight average molecular weight (Mw) of the polylactide in the final composition can be generally at least 10 kg/mol, for example at least 40 kg/mol, for example ranging from 40 to 550 kg/mol, for example from 50 to 350 kg/mol, for example from 50 to 300 kg/mol, and for example from 50 to 200 kg/mol.
The present inventors have shown that a composition comprising lactide and PLA
can be prepared using a melt processes, wherein the typical PLA degassing step can be omitted and the wherein polymerization does not have to be driven to thermodynamic equilibrium.
The present process for preparing lactide and PLA mixture prevents having to mix lactide and PLA via additional extrusion.
Compositions obtainable/obtained by the present process are particularly useful in applications where the composition degrades hydrolytically.
Compositions obtainable/obtained by the present process are also particularly useful in applications related to oil and gas production.
The compositions obtainable/obtained by the present process may be used as diverting agent.
The compositions obtainable/obtained by the present process may also be used as an acid release agent.
The present invention can be further illustrated by the following examples, although it will be understood that these examples are included merely for purposes of illustration and are not intended to limit the scope of the invention unless otherwise specifically indicated.
EXAMPLES
Unless otherwise indicated, all parts and all percentages in the following examples, as well as throughout the specification, are parts by weight or percentages by weight respectively.
Methods Inherent viscosities of the different samples were determined by the following method, compliant with DIN 51562.
12 Solutions of PLA/lactide mixtures were made by weighing a prescribed amount of PLA into a 50 mL flask. 25 mL of chloroform was added after which the flak was shaken in a shaker for at least 4 h, until the sample was visually dissolved. Next, the flask was filled to a volume of exactly 50 mL and was homogenized by hand shaking. The concentration of the sample was chosen from the expected inherent viscosity, guided by the following Table 1.
Table 1: Choice of concentration by expected inherent viscosity Inherent viscosity (dl/g) Concentration (g/dL) flint-, <0.2 2.00 0.02 0.2 Ilion <0.3 1.000 00.2 0.3 Ilion < 1.0 0.500 0.02 nion 1.0 0.1000 0.02 For most samples a concentration of 0.1000 g/dL was taken.
Then 15-20 mL of the solution (or solvent only, for the blank measurement) was placed in an SI Analytical Ubbelohde DIN type Oc glass capillary viscometer (constant K
= 0.003) and placed in a thermostated water bath set and maintained at 25 +/- 0.1 C for at least one hour.
Next, elution times of both the solvent and the solution under investigation were determined in duplicate.
The inherent viscosity in dL/g of the sample is then calculated by formula (1) In 77 rel r 1 inn = (1) wherein c is the concentration of the sample in g/dL and tire, is given by (2) t (2) ?is to wherein ti is the viscosity of the solution and tis is the viscosity of the solvent, t is the elution time of the sample in solution, while to is the elution time of the solvent.
Absolute molecular weight parameters Mo, Mw and polydispersity index PDI were determined using Gel Permeation Chromatography (GPC) on a Viscotek GPC Mx system with 1,1,1,3,3,3-Hexafluoro-2-propanol (hexafluoroisopropanol or HFiP) and 0.02 M
CF3COOK as solvent at a flow rate of 0.7 mL/min. Size exclusion columns were two PSS
PFG analytical linear columns (M, 300 x 8.00 mm, 7 pm) in series.
Table 1: Choice of concentration by expected inherent viscosity Inherent viscosity (dl/g) Concentration (g/dL) flint-, <0.2 2.00 0.02 0.2 Ilion <0.3 1.000 00.2 0.3 Ilion < 1.0 0.500 0.02 nion 1.0 0.1000 0.02 For most samples a concentration of 0.1000 g/dL was taken.
Then 15-20 mL of the solution (or solvent only, for the blank measurement) was placed in an SI Analytical Ubbelohde DIN type Oc glass capillary viscometer (constant K
= 0.003) and placed in a thermostated water bath set and maintained at 25 +/- 0.1 C for at least one hour.
Next, elution times of both the solvent and the solution under investigation were determined in duplicate.
The inherent viscosity in dL/g of the sample is then calculated by formula (1) In 77 rel r 1 inn = (1) wherein c is the concentration of the sample in g/dL and tire, is given by (2) t (2) ?is to wherein ti is the viscosity of the solution and tis is the viscosity of the solvent, t is the elution time of the sample in solution, while to is the elution time of the solvent.
Absolute molecular weight parameters Mo, Mw and polydispersity index PDI were determined using Gel Permeation Chromatography (GPC) on a Viscotek GPC Mx system with 1,1,1,3,3,3-Hexafluoro-2-propanol (hexafluoroisopropanol or HFiP) and 0.02 M
CF3COOK as solvent at a flow rate of 0.7 mL/min. Size exclusion columns were two PSS
PFG analytical linear columns (M, 300 x 8.00 mm, 7 pm) in series.
13 The amount of residual lactide in a sample was determined using a precipitative method where PLA and lactide oligomers are decanted from the solvent containing lactide. Using GC analysis, the amount of lactide in the original sample could then be determined. Those skilled in the art will recognize the possibility to measure the amount of lactide in PLA via various other methods, including 1H-NMR, m-IR, n-IR and Raman spectroscopy.
1. Examples according to the Invention 1.1 Batch polymerization A batch polymerization of L-lactide was performed in a 2 L batch reactor.
First 750 g of L-lactide (PuraLact L, Total Corbion PLA) was allowed to melt at 130 C after which the polymerization was started by addition of 150 ppm of tin octoate (Sigma Aldrich, 92.5-100 %). No co-initiator was used in order to obtain the highest molecular weight possible.
After addition of the tin octoate the reactor was put under 4 bar nitrogen pressure and its contents was heated within 10 min to 180 C. Polymerization was allowed to proceed for 60 min until a conversion of 65 % was reached. The conversion was estimated by observing torque increase, which was correlated to conversion through earlier experiments performed with the same chemicals and settings. The accurate conversion however was measured via the precipitative GC method mentioned. The polymerization was terminated by addition of 1000 ppm of Doverphos S680 (partially hydrolyzed to an acid number of 1.5 mg KOH/g, Dover Chem). After 10 min of further mixing, the highly viscous reactor contents were offloaded using nitrogen pressure into a stainless steel bucket which in turn was placed in ice/water baths to quench the reaction mixture.
1.2 Continuous melt process A continuous melt process was performed using a continuous PLA melt polymerization process. This process was based on static mixers and static reactors and basically comprised a loop reactor, a plug flow reactor and two devolatilization vessels. L-lactide (Puralact L, Total Corbion PLA) was molten and fed at a throughput of 80 kg/h at 130 C into a loop reactor which was heated by an oil-heat transfer unit at 188 C. At the same addition point, 50 ppm of tin octoate (DABCO T-9, Air Products) and 170 g/h of 2-ethyl-1-hexanol (>99.5 % purity, Brenntag) were dosed into the loop reactor. The circulation rate of the loop reactor was 940 kg/h to achieve proper mixing and average residence time was 31 min.
Material was then fed into the plug flow reactor with a residence time of 96 min and temperature was gradually increased to 210 C to decrease material viscosity and plant pressures. Typical process pressures as such were 8-10 bar in the loop reactor and 32-37 bar in the plug flow reactor. At the end of the plug flow reactor 80 g/hr of Adeka Stab AX-71
1. Examples according to the Invention 1.1 Batch polymerization A batch polymerization of L-lactide was performed in a 2 L batch reactor.
First 750 g of L-lactide (PuraLact L, Total Corbion PLA) was allowed to melt at 130 C after which the polymerization was started by addition of 150 ppm of tin octoate (Sigma Aldrich, 92.5-100 %). No co-initiator was used in order to obtain the highest molecular weight possible.
After addition of the tin octoate the reactor was put under 4 bar nitrogen pressure and its contents was heated within 10 min to 180 C. Polymerization was allowed to proceed for 60 min until a conversion of 65 % was reached. The conversion was estimated by observing torque increase, which was correlated to conversion through earlier experiments performed with the same chemicals and settings. The accurate conversion however was measured via the precipitative GC method mentioned. The polymerization was terminated by addition of 1000 ppm of Doverphos S680 (partially hydrolyzed to an acid number of 1.5 mg KOH/g, Dover Chem). After 10 min of further mixing, the highly viscous reactor contents were offloaded using nitrogen pressure into a stainless steel bucket which in turn was placed in ice/water baths to quench the reaction mixture.
1.2 Continuous melt process A continuous melt process was performed using a continuous PLA melt polymerization process. This process was based on static mixers and static reactors and basically comprised a loop reactor, a plug flow reactor and two devolatilization vessels. L-lactide (Puralact L, Total Corbion PLA) was molten and fed at a throughput of 80 kg/h at 130 C into a loop reactor which was heated by an oil-heat transfer unit at 188 C. At the same addition point, 50 ppm of tin octoate (DABCO T-9, Air Products) and 170 g/h of 2-ethyl-1-hexanol (>99.5 % purity, Brenntag) were dosed into the loop reactor. The circulation rate of the loop reactor was 940 kg/h to achieve proper mixing and average residence time was 31 min.
Material was then fed into the plug flow reactor with a residence time of 96 min and temperature was gradually increased to 210 C to decrease material viscosity and plant pressures. Typical process pressures as such were 8-10 bar in the loop reactor and 32-37 bar in the plug flow reactor. At the end of the plug flow reactor 80 g/hr of Adeka Stab AX-71
14 (Adeka Polymer Additives) was added to terminate the polymerization reaction and stabilize the polymer against lactide reformation.
Both devolatilization vessels were kept at atmospheric pressure and material was thereafter pelletized, crystallized at 100 C and dried. Molecular weight of the PLA
pellets such produced was measured by absolute GPO measurements and residual lactide was determined.
Samples were collected and vacuum sealed in moisture-proof bags and subsequently submitted to solution viscosity measurements as described herein above.
The samples generated according to embodiments of the invention have the properties listed in Table 2.
Table 2 Absolute MA, of PLA Lactide Inherent Viscosity Compositions fraction (kg/mol) content (%) (dL/g) Experimental batch 130 35 1.1 Experimental 106 5.4 1.4 continuous 2. Comparative Examples In a Brabender kneader (Type W50E, with Banburry mixers), pre-heated at 180 C, different mixtures of commercial PLA samples (Luminy , Total Corbion PLA by) were melt mixed with L-lactide (Puralact L, Total Corbion PLA by) by kneading to mimic existing extrusion processes that achieve the same, albeit in continuous throughput mode. PLA
pellets were first dried to <250 ppm moisture in a Motan MDE40 desiccant air dryer overnight at 85 C at a dew point of -40 C.
Samples were collected and vacuum sealed in moisture-proof bags and subsequently submitted to solution viscosity measurements as described herein above.
The amount of residual lactide in a sample was determined using a precipitative method where PLA and lactide oligomers are decanted from the solvent containing lactide. Using GC analysis, the amount of lactide in the original sample could then be determined.
These comparative Examples were analyzed and their properties are shown in Table 3.
Table 3: Comparative Examples Absolute MA, of PLA Lactide content Inherent Viscosity Cornposition fraction (kg/mol) (yo) (dL/g) Luminy L105 + Lactide 64 0.42 1.1 Luminy L105 + Lactide 64 7.6 1.0 Luminy L105 + Lactide 64 18 0.9 Luminy L105 + Lactide 64 27 0.8 Luminy L105 + Lactide 64 38 0.7 Luminy L175 + Lactide 120 0.23 1.6 Luminy L175 + Lactide 120 9.6 1.3 Luminy L175 + Lactide 120 19 1.2 Luminy L175 + Lactide 120 28 1.1 Luminy L175 + Lactide 120 38 0.9
Both devolatilization vessels were kept at atmospheric pressure and material was thereafter pelletized, crystallized at 100 C and dried. Molecular weight of the PLA
pellets such produced was measured by absolute GPO measurements and residual lactide was determined.
Samples were collected and vacuum sealed in moisture-proof bags and subsequently submitted to solution viscosity measurements as described herein above.
The samples generated according to embodiments of the invention have the properties listed in Table 2.
Table 2 Absolute MA, of PLA Lactide Inherent Viscosity Compositions fraction (kg/mol) content (%) (dL/g) Experimental batch 130 35 1.1 Experimental 106 5.4 1.4 continuous 2. Comparative Examples In a Brabender kneader (Type W50E, with Banburry mixers), pre-heated at 180 C, different mixtures of commercial PLA samples (Luminy , Total Corbion PLA by) were melt mixed with L-lactide (Puralact L, Total Corbion PLA by) by kneading to mimic existing extrusion processes that achieve the same, albeit in continuous throughput mode. PLA
pellets were first dried to <250 ppm moisture in a Motan MDE40 desiccant air dryer overnight at 85 C at a dew point of -40 C.
Samples were collected and vacuum sealed in moisture-proof bags and subsequently submitted to solution viscosity measurements as described herein above.
The amount of residual lactide in a sample was determined using a precipitative method where PLA and lactide oligomers are decanted from the solvent containing lactide. Using GC analysis, the amount of lactide in the original sample could then be determined.
These comparative Examples were analyzed and their properties are shown in Table 3.
Table 3: Comparative Examples Absolute MA, of PLA Lactide content Inherent Viscosity Cornposition fraction (kg/mol) (yo) (dL/g) Luminy L105 + Lactide 64 0.42 1.1 Luminy L105 + Lactide 64 7.6 1.0 Luminy L105 + Lactide 64 18 0.9 Luminy L105 + Lactide 64 27 0.8 Luminy L105 + Lactide 64 38 0.7 Luminy L175 + Lactide 120 0.23 1.6 Luminy L175 + Lactide 120 9.6 1.3 Luminy L175 + Lactide 120 19 1.2 Luminy L175 + Lactide 120 28 1.1 Luminy L175 + Lactide 120 38 0.9
Claims (15)
1. Process for the preparation of a composition comprising polylactide and lactide by ring-opening polymerization of lactide, said process comprising the steps of : (a) providing lactide and polymerization catalyst to a reactor, (b) melt polymerizing said lactide to a degree of polymerization of at most 96.0 %, to form a composition comprising polylactide and lactide, and (c) removing said composition from the reactor, wherein the whole process is performed at pressures of at least 1 bar, and wherein the composition removed from the reactor is never subjected to a pressure below 1 bar and wherein the composition is not subjected to one of more devolatilization steps.
2. Process according to claim 1, wherein the composition comprises at least 4.0 % by weight of lactide, preferably at least 5.0 % by weight based on the total weight of the composition.
3. Process according to any one of claims 1-2, wherein the polymerization is stopped by addition of a catalyst deactivator.
4. Process according to any one of claims 1-3, wherein the polymerization process is a batch melt process or a continuous melt process.
5. Process according to any one of claims 1-4, comprising the steps of a) continuously providing lactide and polymerization catalyst to a continuous mixing reactor for a first -polymerization, b) continuously removing said first polymerized reaction mixture from the continuous mixing reactor and continuously providing said first polymerized reaction mixture to a plug flow reactor, wherein the reaction mixture is polymerized to a degree of polymerization of at most 96.0 % to form the composition, and c) continuously removing the composition from the plug flow reactor.
6. Process according to claim 5, wherein the first reactor is a loop reactor.
7. Process according to claim 5, wherein the first reactor is a continuously stirred tank reactor
8. Process according to claim 5, wherein the continuous mixing reactor and/or the plug flow reactor is a static mixer reactor.
9. Process according to any one of claims 1-8, wherein the composition removed from the plug flow reactor is not subjected to a devolatilization step, or if one or more devolatilization vessels are used they are kept at a pressure of at least 1 bar.
10. Process according to any one of claims 1-9, wherein the polymerization is performed at a temperature of at least 100 C.
11. Composition directly obtained by a process according to any one of claims 1-10, wherein said composition comprises polylactide and lactide.
12. Use of a composition obtainable by the process of any of the claims 1-11 in applications where the composition degrades hydrolytically.
13. Use of a composition obtainable by the process of any of the claims 1-11 in applications related to oil and gas production.
14. Use of a composition obtainable by the process of any of the claims 1-11 as diverting agent.
15. Use of a composition obtainable by the process of any of the claims 1-11 as an acid release agent.
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